Cytosine: Para-Sulphonato-Calix 4 Arene Assemblies: in Solution, in the Solid-State And

Cytosine: para-sulphonato-calix[4]arene assemblies: in solution, in the solid-state and on the surface of hybrid silver nanoparticles

Yannick Tauran 1,2, Moez Rhimi 3, Ryohei Ueno 4, Marie Grosso 1, Arnaud Brioude 1, Erwann Janneau 5, Kinga Suwinska 6,7,*, Rima Kassab 8, Patrick Shahgaldian9, Alessandro Cumbo 9, Bernard Fenet 10, Beomjoon Kim 2,4 and Anthony W. Coleman 1,*

1 LMI, CNRS UMR 5615 Univ. Lyon 1, Villeurbanne, F69622, France; E-mail: yannick.tauran@ univ-lyon 1.fr

2 LIMMS/CNRS-IIS (UMI 2820), University of Tokyo, Tokyo, Japan; E-mail:

3 BMSSI UMR5086-CNRS/Univ. Lyon 1, Institut de Biologie et Chimie des Proteines FR3302, 7 Passage du Vercors, Lyon, F69367, France; E-mail:

4 CIRMM, Institute of Industrial Science, University of Tokyo, Tokyo, Japan; E-mail:

5 Centre de diffractométrie Henri Longchambon, Univ. Lyon 1, Villeurbanne, F69622, France; E-mail:

6 Institute of Physical Chemistry, Polish Academy of Sciences, Kasprzaka 44/52, PL-01 224 Warszawa, Poland; E-mail:

7 Faculty of Biology and Environmental Sciences, Cardinal Stefan, Wyszynski University in Warsaw, Wo´ycickiego 1/3, PL-01938, Warszawa, Poland;

8 University of Balamand, Faculty of Sciences- Department of Chemistry P.O Box: 100 –Tripoli-Lebanon; E-mail :

9 Fachhochschule Nordwestschweiz, Hochschule für Lifesciences, Gründenstrasse 40, 4132 Muttenz, Switzerland; E-mail :

10 Centre Commun RMN, Univ. Lyon 1, Villeurbanne, F69622 France; E-mail :

* Dr Antony W. Coleman; E-Mail: -lyon 1.fr;
Tel.: +33 4-42-43-10-27; Fax: +33 4-72-44 -06-18.

* Dr Kinga Suwinska; E-Mail: ;
Tel.: +48-22343-3399

Supporting Information

Figure S1 A graph of the 1/ΔIf vs. 1/[H]0 for cytosine / para-sulphonato-calix[4]arene complex with n= 0,5

Figure S2 A graph of the 1/ΔIf vs. 1/[H]0 for cytosine / para –sulphonato-calix[4]arene complex with n= 2

Figure S3 A graph of the 1/ΔIf vs. 1/[H]0 for cytosine / para-sulphonato-calix[4]arene silver nanoparticles with n= 1

Figure S4 A graph of the 1/ΔIf vs. 1/[H]0 for cytosine / para-sulphonato-calix[4]arene silver nanoparticles with n= 2

Figure S5 TEM picture of para-sulphonato-calix[4]arene capped silver nanoparticles. The black bar represent 100 nm.

TEM Imaging protocole:

The TEM sample was prepared by dropping 6 μL of 1.10-4M solution of para-sulphonato-calix[4]arene capped silver nanoparticles on carbon coated grid (50 mesh, Ted Pella). After 30 seconds, the sample was wicked from the grid by touching its edge with a piece of filter paper. TEM studies were conducted by using a Topcon EM 002B microscope, operating with an accelerating voltage of 200 kV.

Diffusion NMR experiments

Table S1 List of calculated Ka from diffusion coefficients of the complex cytosine / para-sulphonato-calix[4]arene

cytosine concentration (mM) / 0,92 / 0,84 / 0,78 / 0,77 / 0,74
para-sulphonato-calix[4]arene
concentration (mM) / 0,09 / 0,41 / 0,92 / 4,46 / 8,32
cytosine diffusion
coefficient (10-6 cm2s-1) / 7,545 / 6,368 / 5,521 / 4,087 / 3,688
para-sulphonato-calix[4]arene
diffusion coefficient (10-6 cm2s-1) / 3,175 / 3,2855 / 3,3375 / 3,2555 / 3,1805
Mole fraction of the complex / 0,0422 / 0,3059 / 0,4956 / 0,8169 / 0,9063
Ka (M-1) / 862,09 / 2880,41 / 1842,82 / 1165,06 / 1265,24

Crystal data

2(C28H20O16S4)·8(C4H6N3O)·CH4O·18(H2O) / Z = 1
Mr = 2734.71 / F(000) = 1430.000
Triclinic, P¯1 / Dx = 1.595 Mg m-3
Hall symbol: -P 1 / Mo Ka radiation, l = 0.7107 Å
a = 12.423 (1) Å / Cell parameters from 7049 reflections
b = 14.894 (2) Å / q = 3.4–29.4°
c = 17.357 (1) Å / m = 0.27 mm-1
a = 71.444 (9)° / T = 100 K
b = 71.745 (8)° / Block, colorless
g = 75.420 (9)° / 0.33 × 0.19 × 0.15 mm
V = 2849.8 (5) Å3

Data collection

Xcalibur, Atlas, Gemini ultra
diffractometer / 12946 independent reflections
Radiation source: Enhance (Mo) X-ray Source / 9331 reflections with I > 2.0s(I)
graphite / Rint = 0.058
Detector resolution: 10.4685 pixels mm-1 / qmax = 29.5°, qmin = 3.4°
w scans / h = -15®15
Absorption correction: analytical
CrysAlis PRO, Agilent Technologies, Version 1.171.35.21 (release 20-01-2012 CrysAlis171 .NET) (compiled Jan 23 2012,18:06:46) Analytical numeric absorption correction using a multifaceted crystal model based on expressions derived by R.C. Clark & J.S. Reid. (Clark, R. C. & Reid, J. S. (1995). Acta Cryst. A51, 887-897) / k = -17®19
Tmin = 0.943, Tmax = 0.970 / l = 0®23
25103 measured reflections

Refinement

Refinement on F2 / Hydrogen site location: difference Fourier map
Least-squares matrix: full / H-atom parameters constrained
R[F2 > 2s(F2)] = 0.067 / Method, part 1, Chebychev polynomial, (Watkin, 1994, Prince, 1982) [weight] = 1.0/[A0*T0(x) + A1*T1(x) ···+ An-1]*Tn-1(x)]
where Ai are the Chebychev coefficients listed below and x = F /Fmax Method = Robust Weighting (Prince, 1982) W = [weight] * [1-(deltaF/6*sigmaF)2]2 Ai are: 674. 0.107E + 04 607. 216. 37.8
wR(F2) = 0.196 / (D/s)max = 0.002
S = 0.90 / Dñmax = 1.87 e Å-3
12946 reflections / Dñmin = -1.15 e Å-3
884 parameters / Extinction correction: Larson (1970), Equation 22
45 restraints / Extinction coefficient: 43 (9)
Primary atom site location: structure-invariant direct methods

Fractional atomic coordinates and isotropic or equivalent isotropic displacement parameters (Å2)

x / y / z / Uiso*/Ueq / Occ. (<1)
S1 / 0.58225 (8) / 0.29029 (6) / 0.69870 (6) / 0.0151
O2 / 0.6558 (3) / 0.3322 (2) / 0.72241 (18) / 0.0233
O3 / 0.4605 (2) / 0.3103 (2) / 0.74307 (17) / 0.0214
O4 / 0.6210 (2) / 0.18665 (19) / 0.70693 (17) / 0.0198
C5 / 0.5921 (3) / 0.3434 (2) / 0.5907 (2) / 0.0141
C6 / 0.6501 (3) / 0.4203 (2) / 0.5459 (2) / 0.0131
C7 / 0.6548 (3) / 0.4604 (2) / 0.4607 (2) / 0.0123
C8 / 0.6005 (3) / 0.4219 (3) / 0.4218 (2) / 0.0132
O9 / 0.6080 (2) / 0.46400 (19) / 0.33924 (16) / 0.0171
H91 / 0.5675 / 0.4492 / 0.3178 / 0.0263*
C10 / 0.5423 (3) / 0.3442 (3) / 0.4671 (2) / 0.0148
C11 / 0.5395 (3) / 0.3057 (2) / 0.5515 (2) / 0.0139
H111 / 0.5015 / 0.2539 / 0.5825 / 0.0170*
C12 / 0.4877 (3) / 0.2991 (3) / 0.4255 (2) / 0.0159
C13 / 0.5801 (3) / 0.2425 (3) / 0.3692 (2) / 0.0157
C14 / 0.6395 (3) / 0.1551 (3) / 0.4046 (2) / 0.0180
C15 / 0.7264 (3) / 0.1028 (3) / 0.3538 (3) / 0.0198
S16 / 0.79747 (9) / -0.00998 (7) / 0.40228 (7) / 0.0224
O17 / 0.7102 (3) / -0.0624 (2) / 0.4610 (2) / 0.0289
O18 / 0.8661 (4) / -0.0554 (2) / 0.3362 (3) / 0.0652
O19 / 0.8650 (4) / 0.0117 (3) / 0.4473 (4) / 0.0673
C20 / 0.7542 (3) / 0.1399 (3) / 0.2673 (3) / 0.0189
C21 / 0.6977 (3) / 0.2285 (3) / 0.2294 (2) / 0.0168
C22 / 0.6092 (3) / 0.2797 (3) / 0.2815 (2) / 0.0163
O23 / 0.5457 (2) / 0.3661 (2) / 0.25244 (17) / 0.0195
H231 / 0.5654 / 0.3850 / 0.2013 / 0.0286*
C24 / 0.7374 (3) / 0.2684 (3) / 0.1345 (2) / 0.0187
C25 / 0.8521 (3) / 0.3014 (3) / 0.1110 (2) / 0.0162
C26 / 0.8586 (3) / 0.3884 (3) / 0.1227 (2) / 0.0164
O27 / 0.7561 (2) / 0.4420 (2) / 0.15120 (18) / 0.0200
H271 / 0.7500 / 0.4900 / 0.1656 / 0.0302*
C28 / 0.9649 (3) / 0.4168 (3) / 0.1062 (2) / 0.0146
C29 / 1.0656 (3) / 0.3548 (3) / 0.0791 (2) / 0.0150
C30 / 1.0593 (3) / 0.2684 (3) / 0.0681 (2) / 0.0169
C31 / 0.9527 (3) / 0.2414 (3) / 0.0841 (2) / 0.0156
H311 / 0.9493 / 0.1817 / 0.0775 / 0.0189*
S32 / 1.18356 (8) / 0.18304 (6) / 0.04277 (6) / 0.0154
O33 / 1.2838 (2) / 0.2286 (2) / 0.02315 (18) / 0.0209
O34 / 1.1743 (2) / 0.1590 (2) / -0.02969 (17) / 0.0208
O35 / 1.1787 (3) / 0.1016 (2) / 0.11668 (18) / 0.0223
H291 / 1.1371 / 0.3719 / 0.0684 / 0.0180*
C36 / 0.9727 (3) / 0.5091 (3) / 0.1222 (2) / 0.0158
C37 / 0.9564 (3) / 0.4984 (2) / 0.2150 (2) / 0.0134
C38 / 0.8494 (3) / 0.5307 (2) / 0.2660 (2) / 0.0126
O39 / 0.7655 (2) / 0.57936 (18) / 0.22451 (16) / 0.0153
H391 / 0.7005 / 0.5869 / 0.2551 / 0.0232*
C40 / 0.8320 (3) / 0.5156 (2) / 0.3525 (2) / 0.0146
C41 / 0.7168 (3) / 0.5445 (2) / 0.4108 (2) / 0.0139
H411 / 0.7314 / 0.5711 / 0.4504 / 0.0174*
H412 / 0.6690 / 0.5932 / 0.3781 / 0.0169*
C42 / 0.9264 (3) / 0.4727 (2) / 0.3869 (2) / 0.0133
C43 / 1.0330 (3) / 0.4433 (2) / 0.3370 (2) / 0.0128
C44 / 1.0482 (3) / 0.4540 (2) / 0.2519 (2) / 0.0136
H441 / 1.1204 / 0.4330 / 0.2193 / 0.0159*
S45 / 1.15040 (7) / 0.39463 (6) / 0.38387 (5) / 0.0130
O46 / 1.1575 (2) / 0.4646 (2) / 0.42237 (18) / 0.0202
O47 / 1.2519 (2) / 0.37717 (19) / 0.31556 (17) / 0.0172
O48 / 1.1240 (2) / 0.30370 (19) / 0.44469 (17) / 0.0181
H421 / 0.9177 / 0.4634 / 0.4444 / 0.0158*
H361 / 1.0494 / 0.5249 / 0.0919 / 0.0188*
H362 / 0.9159 / 0.5609 / 0.1010 / 0.0185*
H242 / 0.6811 / 0.3224 / 0.1151 / 0.0223*
H241 / 0.7460 / 0.2184 / 0.1075 / 0.0218*
H201 / 0.8115 / 0.1045 / 0.2339 / 0.0228*
H141 / 0.6223 / 0.1300 / 0.4627 / 0.0216*
H122 / 0.4400 / 0.2546 / 0.4686 / 0.0188*
H121 / 0.4401 / 0.3479 / 0.3924 / 0.0191*
H61 / 0.6854 / 0.4448 / 0.5727 / 0.0149*
O49 / 0.3225 (2) / 0.1653 (2) / 0.81735 (17) / 0.0185
H491 / 0.2987 / 0.1617 / 0.8677 / 0.0280*
H492 / 0.3625 / 0.2075 / 0.7957 / 0.0280*
O50 / 0.6712 (2) / 0.4623 (2) / 0.79953 (18) / 0.0213
H501 / 0.6931 / 0.5091 / 0.7626 / 0.0322*
H502 / 0.6623 / 0.4283 / 0.7751 / 0.0323*
O51 / 0.2843 (2) / 0.2282 (2) / 0.61944 (18) / 0.0202
C52 / 0.1833 (3) / 0.2514 (2) / 0.6529 (2) / 0.0155
N53 / 0.1451 (3) / 0.2425 (2) / 0.7393 (2) / 0.0146
C54 / 0.0358 (3) / 0.2725 (2) / 0.7805 (2) / 0.0156
N55 / 0.0103 (3) / 0.2618 (2) / 0.8620 (2) / 0.0184
H551 / -0.0579 / 0.2819 / 0.8884 / 0.0221*
H552 / 0.0635 / 0.2408 / 0.8887 / 0.0221*
C56 / -0.0471 (3) / 0.3129 (3) / 0.7324 (2) / 0.0167
C57 / -0.0128 (3) / 0.3184 (3) / 0.6499 (2) / 0.0185
N58 / 0.0984 (3) / 0.2873 (2) / 0.6109 (2) / 0.0163
H581 / 0.1179 / 0.2960 / 0.5571 / 0.0202*
H571 / -0.0664 / 0.3437 / 0.6183 / 0.0222*
H561 / -0.1230 / 0.3343 / 0.7577 / 0.0196*
H531 / 0.1950 / 0.2202 / 0.7672 / 0.0171*
O59 / 0.4299 (3) / 0.8806 (2) / 0.88440 (19) / 0.0269
C60 / 0.4600 (3) / 0.9083 (3) / 0.8080 (3) / 0.0195
N61 / 0.4173 (3) / 0.9968 (2) / 0.7636 (2) / 0.0207
C62 / 0.4481 (4) / 1.0267 (3) / 0.6785 (3) / 0.0223
C63 / 0.5259 (3) / 0.9700 (3) / 0.6319 (3) / 0.0211
C64 / 0.5770 (3) / 0.8789 (3) / 0.6747 (2) / 0.0169
N65 / 0.5412 (3) / 0.8514 (2) / 0.7595 (2) / 0.0194
H651 / 0.5805 / 0.8010 / 0.7856 / 0.0231*
N66 / 0.6578 (3) / 0.8214 (2) / 0.6351 (2) / 0.0193
H662 / 0.6864 / 0.7657 / 0.6624 / 0.0230*
H661 / 0.6844 / 0.8408 / 0.5824 / 0.0231*
H631 / 0.5460 / 0.9902 / 0.5738 / 0.0261*
H621 / 0.4142 / 1.0872 / 0.6519 / 0.0270*
H611 / 0.3741 / 1.0373 / 0.7913 / 0.0245*
O67 / 1.0774 (3) / -0.0031 (2) / 0.89558 (19) / 0.0239
C68 / 0.9827 (3) / 0.0370 (3) / 0.8841 (3) / 0.0194
N69 / 0.9660 (3) / 0.0670 (2) / 0.8044 (2) / 0.0186
C70 / 0.8630 (4) / 0.1083 (3) / 0.7865 (3) / 0.0198
N71 / 0.8568 (3) / 0.1290 (3) / 0.7092 (2) / 0.0233
H711 / 0.7914 / 0.1523 / 0.6969 / 0.0280*
H712 / 0.9153 / 0.1117 / 0.6707 / 0.0283*
C72 / 0.7673 (4) / 0.1284 (3) / 0.8533 (3) / 0.0227
C73 / 0.7828 (4) / 0.0998 (3) / 0.9314 (3) / 0.0240
N74 / 0.8880 (3) / 0.0564 (2) / 0.9458 (2) / 0.0210
H741 / 0.8929 / 0.0331 / 0.9967 / 0.0249*
H731 / 0.7205 / 0.1088 / 0.9773 / 0.0285*
H721 / 0.6962 / 0.1599 / 0.8432 / 0.0270*
H691 / 1.0250 / 0.0587 / 0.7631 / 0.0221*
O75 / 0.2186 (3) / 0.6453 (2) / 0.07916 (18) / 0.0234
H751 / 0.2420 / 0.6120 / 0.1202 / 0.0349*
H752 / 0.2714 / 0.6734 / 0.0475 / 0.0350*
O76 / 0.4187 (3) / 0.3554 (2) / 0.9008 (2) / 0.0276
H761 / 0.3671 / 0.3219 / 0.9306 / 0.0412*
H762 / 0.4360 / 0.3460 / 0.8551 / 0.0410*
O77 / 0.6777 (3) / 0.7147 (2) / 0.8474 (2) / 0.0321
H771 / 0.6733 / 0.6577 / 0.8695 / 0.0482*
H772 / 0.6831 / 0.7352 / 0.8844 / 0.0480*
O78 / 0.2930 (3) / 0.4631 (2) / 0.0374 (2) / 0.0346
H781 / 0.3441 / 0.4747 / -0.0060 / 0.0512*
H782 / 0.2683 / 0.5139 / 0.0509 / 0.0514*
O79 / 0.5670 (3) / 0.3060 (3) / 0.0037 (2) / 0.0424
H791 / 0.5683 / 0.2520 / 0.0358 / 0.0472*
H792 / 0.5234 / 0.3205 / -0.0270 / 0.0472*
O80 / 0.5242 (3) / 0.4501 (3) / 0.0974 (2) / 0.0374
H801 / 0.4760 / 0.4879 / 0.1203 / 0.0551*
H802 / 0.4923 / 0.4346 / 0.0699 / 0.0545*
O81 / 0.1208 (6) / 0.7929 (5) / 0.4655 (4) / 0.0336 / 0.6638
O82 / 0.0868 (13) / 0.8237 (10) / 0.4572 (9) / 0.0295 / 0.3362
C83 / 0.0701 (4) / 0.8058 (3) / 0.5345 (3) / 0.0244
N84 / -0.0234 (6) / 0.8735 (5) / 0.5486 (4) / 0.0185 / 0.6638
N85 / -0.0294 (13) / 0.8555 (11) / 0.5817 (8) / 0.0195 / 0.3362
C86 / -0.0840 (6) / 0.8905 (5) / 0.6242 (4) / 0.0219 / 0.6638
H851 / -0.0865 / 0.8800 / 0.5592 / 0.0212* / 0.3362
C87 / -0.0501 (15) / 0.8461 (12) / 0.6647 (11) / 0.0200 / 0.3362
N88 / -0.1366 (10) / 0.8982 (8) / 0.7038 (7) / 0.0263 / 0.3362
C89 / -0.0442 (8) / 0.8306 (7) / 0.6955 (6) / 0.0277 / 0.6638
H891 / -0.0814 / 0.8387 / 0.7492 / 0.0359* / 0.6638
C90 / 0.0493 (9) / 0.7622 (6) / 0.6843 (5) / 0.0248 / 0.6638
C91 / 0.0282 (19) / 0.7782 (15) / 0.7074 (12) / 0.0252 / 0.3362
C92 / 0.1209 (13) / 0.7273 (9) / 0.6642 (8) / 0.0238 / 0.3362
H901 / 0.0753 / 0.7218 / 0.7305 / 0.0298* / 0.6638
N93 / 0.1061 (7) / 0.7496 (7) / 0.6056 (6) / 0.0275 / 0.6638
N94 / 0.1398 (15) / 0.7423 (15) / 0.5810 (13) / 0.0270 / 0.3362
H931 / 0.1550 / 0.6976 / 0.6027 / 0.0302* / 0.6638
H941 / 0.2012 / 0.7104 / 0.5550 / 0.0242* / 0.3362
H921 / 0.1711 / 0.6808 / 0.6924 / 0.0280* / 0.3362
H911 / 0.0192 / 0.7697 / 0.7645 / 0.0322* / 0.3362
N95 / -0.1717 (5) / 0.9609 (4) / 0.6273 (4) / 0.0277 / 0.6638
H882 / -0.1968 / 0.9203 / 0.6848 / 0.0320* / 0.3362
H951 / -0.2106 / 0.9722 / 0.6748 / 0.0600* / 0.6638
H952 / -0.1904 / 0.9958 / 0.5819 / 0.0600* / 0.6638
H881 / -0.1402 / 0.9016 / 0.7532 / 0.0320* / 0.3362
H841 / -0.0487 / 0.9080 / 0.5055 / 0.0258* / 0.6638
O96 / 0.6710 (4) / 0.9839 (3) / 0.7782 (3) / 0.0512
H961 / 0.7138 / 0.9639 / 0.8106 / 0.0764*
H962 / 0.6386 / 1.0377 / 0.7837 / 0.0764*
O97 / 0.4986 (7) / 0.8884 (6) / 0.0535 (5) / 0.0450 / 0.5000
C98 / 0.500000 (10) / 1.000000 (10) / 0.000000 (10) / 0.0634
H985 / 0.5550 / 1.0249 / 0.0129 / 0.0960* / 0.5000
H984 / 0.5214 / 1.0037 / -0.0591 / 0.0960* / 0.5000
H986 / 0.5756 / 0.9631 / -0.0151 / 0.0960* / 0.5000
H971 / 0.5555 / 0.8546 / 0.0314 / 0.0680* / 0.5000

Atomic displacement parameters (Å2)